JP5975870B2 - Compound for organic optoelectronic device, organic light emitting diode including the same, and display device including the organic light emitting diode - Google Patents

Description

This description is an organic photoelectric child element compound, an organic light emitting diode containing the same, and a display device including the organic light emitting diode.

Photoelectron element (opto electric device) is to convert light energy into electrical energy in a broad sense, it is a device that converts electrical energy into light energy. The photoelectron device, an organic light emitting diode (OLED: Organic-Light Emitting Diodes ), solar cells, and as an example, such as a transistor. In particular, organic light emitting diodes have attracted attention in recent years as demand for flat panel displays increases.

  When an electric current is applied to the organic light emitting diode, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons move to the respective hole transport layer (HTL) and electron transport layer (ETL) to emit light. Recombination in the layers forms luminescent excitons. The luminescence excitons thus formed emit light while transitioning to the ground state. The light is divided into fluorescence using singlet excitons and phosphorescence using triplet excitons according to an emission mechanism, and the fluorescence and phosphorescence can be used as a light emitting source of an organic light emitting diode (DFO '). Brien, Appl. Phys. Lett., 74 (3), 442, 1999; MA Baldo, Appl. Phys. Lett., 75 (1), 4, 1999).

  When an electron transitions from a ground state to an excited state, a singlet exciton is non-radiatively transferred to a triplet exciton through intersystem crossing, and the triplet exciton again transitions to a ground state to emit light. To do. The light emission at this time is called phosphorescence light emission. The triplet exciton cannot make a direct transition to the ground state, and must pass through an electron spin flipping step. Therefore, phosphorescence has a characteristic that it has a longer half-life (emission time, lifetime) than fluorescence.

  When holes and electrons are recombined to form luminescent excitons, triplet excitons are generated about three times as many as singlet excitons. The fluorescent material has a singlet excited state of 25% and has a limited light emission efficiency. However, phosphorescence can be used up to a generation probability of triplet excitons of 75% and a singlet excited state of 25%, and the theoretical internal quantum efficiency is 100%. That is, the phosphorescent material has an advantage that it can achieve luminous efficiency about four times larger than that of the fluorescent material.

  Meanwhile, both a host material and a dopant can be added to the light emitting layer to increase the efficiency and stability of the organic light emitting diode. As the host material, 4,4'-N, N'-dicarbazole biphenyl (CBP) was mainly used. However, since CBP has very high structural symmetry, it is easy to crystallize and has low thermal stability. Therefore, short circuit and pixel defects occur during the heat resistance test of the device. In addition, since most host materials such as CBP have a hole moving speed higher than an electron moving speed, excitons are efficiently formed in the light emitting layer, and the light emitting efficiency of the device is reduced. .

  In addition, since the low molecular weight host material generally uses a vacuum deposition method, it has a disadvantage in that the manufacturing cost is higher than that of a wet process. In addition, since most low-molecular host materials have low solubility in organic solvents, they cannot be applied to the wet process and an organic thin film layer having excellent film characteristics cannot be formed.

Therefore, in order to realize an excellent organic light electronic device efficiency and lifetime, electrical, excellent thermal stability, phosphorescent host material having a bipolar property of holes and electrons can be all transmitted well In addition, it is necessary to develop a charge transport material and to develop a host material that can be used by mixing a material that can transmit holes and electrons well.

An embodiment of the present invention is excellent in thermal stability, to provide an organic photoelectric child element compound for all holes and electrons can be transmitted well.

Another embodiment of the present invention provides an organic light emitting diode with excellent efficiency and the driving voltage characteristic including the organic photoelectric child element compound.

Still another embodiment of the present invention provides a display device including the organic light emitting diode .

According to an embodiment of the present invention, an organic photoelectric child element compound having a substituent represented by Formulas 1 and 2 below are provided.

In Formulas 1 and 2,
L is a divalent to 7-valent linking group, and is an oxide group, amine group, phosphonyl group, phosphonate group, sulfonyl group, sulfonate group, substituted or unsubstituted C1-C30 alkylene group, substituted Or an unsubstituted C1-C30 heteroalkylene group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted A C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof,
R ¹ and R ² are the same or different from each other, and each independently represents hydrogen, a carbazolyl group, a C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, C2-C30 A heteroaryl group, a C6-C30 arylamine group, or a combination thereof,
R ^{3 to} R ⁵ are the same as or different from each other, and each independently represents hydrogen, a carbazolyl group, a C1-C30 alkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a C6- An arylamine group of C30 or a combination thereof,
a is an integer of 2-5.

In particular, R ¹ and R ² may be the same or different from each other, and each independently represents a carbazolyl group, a C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, C2- A heteroaryl group of C30 or a combination thereof, and R ^{3 to} R ⁵ are the same or different from each other, and each independently represents hydrogen, a C1-C30 alkyl group, a C6-C30 aryl group, or these A combination of these may be used.

  The chemical formula 1 may be represented by the following chemical formula 1a.

In Formula 1a,
Ra ¹ and Ra ² are the same or different from each other, and each independently represents hydrogen or a C1-C10 alkyl group,
R ³ is hydrogen, a carbazolyl group, a C1-C30 alkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a C6-C30 arylamine group, or a combination thereof.

  The chemical formula 2 may be represented by any of the following chemical formulas 2a to 2c.

In the chemical formulas 2a to 2c,
L is a divalent to 7-valent linking group, and is an oxide group, amine group, phosphonyl group, phosphonate group, sulfonyl group, sulfonate group, substituted or unsubstituted C1-C30 alkylene group, substituted Or an unsubstituted C1-C30 heteroalkylene group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted A C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof,
R ⁴ and R ⁵ are the same or different from each other, and are independently hydrogen, carbazolyl group, C1-C30 alkyl group, C6-C30 aryl group, C2-C30 heteroaryl group, C6- An arylamine group of C30 or a combination thereof,
a is an integer of 2-5.

  In addition, L in Chemical Formula 2 may be a divalent to 7-valent linking group derived from a compound represented by the following Chemical Formulas 2d to 2j or a combination thereof.

In the chemical formulas 2d to 2j,
Q ^{1 to} Q ⁶ are the same or different from each other, and each independently represents a substituted or unsubstituted N atom, a substituted or unsubstituted P atom, or a substituted or unsubstituted S atom. A substituted or unsubstituted O atom, a substituted or unsubstituted C atom, or a combination thereof, wherein the “substituted” means hydrogen, an oxide group, a cyano group, a halogen group, A C1-C30 alkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group or a combination thereof is meant.

  In Formula 2, a may be 2 or 3.

  L in Formula 2 may be represented by the following Formula 2k.

Moreover, the organic photoelectric child element compound may be represented by Chemical Formula 3 to Formula 8 below.

In the chemical formulas 3 to 8,
L is a divalent to 7-valent linking group, and is an oxide group, amine group, phosphonyl group, phosphonate group, sulfonyl group, sulfonate group, substituted or unsubstituted C1-C30 alkylene group, substituted Or an unsubstituted C1-C30 heteroalkylene group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted A C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof,
R ^{1 to} R ¹⁰ are the same as or different from each other, and each independently represents hydrogen, a carbazolyl group, a C1-C30 alkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a C6- A C30 arylamine group or a combination thereof.

Moreover, the organic photoelectric child element compound may be represented by Chemical Formula 9 to Formula 33 below.

The organic photoelectric child element compound may be used as a charge transporting material or the host material, the thermal decomposition temperature (T _d) may be 350 to 600 ° C..

According to another embodiment of the present invention, an anode, a cathode, and wherein comprises at least one organic thin layer disposed between the anode and the cathode, the organic thin film layer, the organic light electronic elements for compound An organic light emitting diode is provided.

  The organic thin film layer includes a light emitting layer, a hole blocking layer, an electron transport layer (ETL), an electron injection layer (EIL), a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer, or these It may be a combination.

According to still another embodiment of the present invention, a display device including the organic light emitting diode is provided.

  Other specific matters of the embodiment of the present invention are described in the following detailed description.

Organic photoelectric child element compound according to an embodiment of the present invention has a superior thermal stability, especially, has a high luminous efficiency even at a low driving voltage is used in the organic thin film layer of an organic light electronic device, life to provide an organic light electronic device and a display device with improved.

The organic light emitting diode comprising an organic light electronic elements for compounds according to various embodiments of the present invention is a cross-sectional view illustrating. The organic light emitting diode comprising an organic light electronic elements for compounds according to various embodiments of the present invention is a cross-sectional view illustrating. The organic light emitting diode comprising an organic light electronic elements for compounds according to various embodiments of the present invention is a cross-sectional view illustrating. The organic light emitting diode comprising an organic light electronic elements for compounds according to various embodiments of the present invention is a cross-sectional view illustrating. The organic light emitting diode comprising an organic light electronic elements for compounds according to various embodiments of the present invention is a cross-sectional view illustrating. 6 is a graph showing changes in current density according to voltage of organic light emitting diodes manufactured in Example 3 and Comparative Example 1. 5 is a graph showing a change in luminance according to voltage of organic light emitting diodes manufactured in Example 3 and Comparative Example 1. 6 is a graph showing changes in current efficiency depending on luminance of organic light emitting diodes manufactured in Example 3 and Comparative Example 1. 6 is a graph showing changes in power efficiency depending on luminance of organic light emitting diodes manufactured in Example 3 and Comparative Example 1.

  Hereinafter, exemplary embodiments of the present invention will be described in detail. However, these embodiments are merely examples, and the present invention is not limited thereto, and is defined by the description of the scope of claims.

  In the present specification, the term “substituted” is a halogen group, a cyano group, a C1-C30 alkyl group, a C3-C30 cycloalkyl group, a C6-C30 aryl group, a C1-C30 unless otherwise defined. A C30 alkoxy group or a combination thereof is meant.

  In this specification, the term “halogen group” means a halogen group of a fluoro group, a chloro group, a bromo group, or a combination thereof unless otherwise defined, and it is particularly preferable to use a fluoro group.

  As used herein, the term “hetero” means one containing 1-3 N, P, S, or O, with the remainder being carbon, unless otherwise defined.

  In the present specification, the term “a combination thereof” means that two or more substituents are bonded by a single bond or two or more substituents are condensed and bonded unless otherwise defined. Means.

According to an embodiment of the present invention, an organic photoelectric child element compound for the substituent is bonded to Formula 1 and 2 below are provided.

In Formulas 1 and 2,
L is a divalent to 7-valent linking group, and is an oxide group, amine group, phosphonyl group, phosphonate group, sulfonyl group, sulfonate group, substituted or unsubstituted C1-C30 alkylene group, substituted Or an unsubstituted C1-C30 heteroalkylene group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted A C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof. At this time, examples of the heterocycloalkylene include substituents such as pyrrolidine, tetrahydrofuran, tetrahydrothiophene, dioxane, dithiane, and examples of the heteroarylene include thiophene, furan, pyrrole, imidazole, thiazole, oxazole, Substituents such as oxadiazole, thiadiazole, triazole, triazine, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, and the like. , Fluorene, fluorenone, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, oxanthrene, thianthrene and the like. However, L is not limited to the above example.

R ^{1 to} R ⁵ are the same as or different from each other, and each independently represents hydrogen, a carbazolyl group, a C1-C30 alkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a C6- A C30 arylamine group or a combination thereof, in particular, the R ¹ and R ² are the same or different from each other, and each independently represents a carbazolyl group, a C1-C30 alkyl group, a C6-C30 An aryl group, a C2-C30 heteroaryl group, or a combination thereof, and R ^{3 to} R ⁵ are the same or different from each other, and each independently represents hydrogen, a C1-C30 alkyl group, or a C6-C30. Or a combination thereof.

When R ^{1 to} R ⁵ are C6 to C30 aryl groups, the aryl group is a phenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a tetracene group, a pyrene group, a fluorene group, or a combination thereof. May be. However, the aryl group is not limited to the above example.

When R ^{1 to} R ⁵ are C2-C30 heteroaryl groups, the heteroaryl groups are thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, thiadiazole, triazole, triazine, pyridine, It may be pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline or a combination thereof. However, the heteroaryl group is not limited to the above examples.

  a is an integer of 2 to 5, and each repeating unit may be the same as or different from each other.

  The chemical formula 1 may be represented by the following chemical formula 1a.

In Formula 1a,
Ra ¹ and Ra ² are the same or different from each other, and each independently represents hydrogen or a C1-C10 alkyl group,
R ³ is hydrogen, a carbazolyl group, a C1-C30 alkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a C6-C30 arylamine group, or a combination thereof.

  The chemical formula 2 may be represented by any of the following chemical formulas 2a to 2c.

In the chemical formulas 2a to 2c,
L is a divalent to 7-valent linking group, and is an oxide group, amine group, phosphonyl group, phosphonate group, sulfonyl group, sulfonate group, substituted or unsubstituted C1-C30 alkylene group, substituted Or an unsubstituted C1-C30 heteroalkylene group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted A C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof,
R ⁴ and R ⁵ are the same or different from each other, and are independently hydrogen, carbazolyl group, C1-C30 alkyl group, C6-C30 aryl group, C2-C30 heteroaryl group, C6- An arylamine group of C30 or a combination thereof,
a is an integer of 2-5.

  In addition, L in Chemical Formula 2 may be a divalent to 7-valent linking group derived from a compound represented by the following Chemical Formulas 2d to 2j or a combination thereof.

In the chemical formulas 2d to 2j,
Q ^{1 to} Q ⁶ are the same or different from each other, and each independently represents a substituted or unsubstituted N atom, a substituted or unsubstituted P atom, or a substituted or unsubstituted S atom. Substituted or unsubstituted O atom, substituted or unsubstituted C atom or a combination thereof, wherein the substitution is hydrogen, oxide group, cyano group, halogen group, C1-C30 alkyl A C6-C30 aryl group, a C2-C30 heteroaryl group, or a combination thereof.

  In the chemical formula 2, a may be 2 or 3.

  In addition, L in the chemical formula 2 may be represented by the chemical formula 2k. However, the L is not limited to these.

Moreover, the organic photoelectric child element compound may be represented by Formula 3 Formula 8 below.

In the chemical formulas 3 to 8,
L is a divalent to 7-valent linking group, and is an oxide group, amine group, phosphonyl group, phosphonate group, sulfonyl group, sulfonate group, substituted or unsubstituted C1-C30 alkylene group, substituted Or an unsubstituted C1-C30 heteroalkylene group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C1-C30 heterocycloalkylene group, a substituted or unsubstituted A C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof,
R ^{1 to} R ¹⁰ are the same as or different from each other, and each independently represents hydrogen, a carbazolyl group, a C1-C30 alkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a C6- A C30 arylamine group or a combination thereof.

Moreover, the organic photoelectric child element compound may be represented by Chemical Formula 9 to Formula 33 below. However, the organic photoelectric child element compound is not limited thereto.

The organic photoelectric child element compound may be used as a charge transporting material or the host material, in particular, the organic photoelectric child-element compound in the phosphorescent host material when used as a host material, an organic photoelectric child The driving voltage of the element can be lowered and the light emission efficiency can be improved.

Further, when said organic photoelectric child-element compound is used as a host material, the organic photoelectric child element compound for use in mixing or blending with low molecular weight host material or polymeric host materials commonly used in the art May be. In some cases, polyvinyl carbazole, polycarbonate, polyester, polyarylate, polystyrene, acrylic polymer, methacrylic polymer, polybutyral, polyvinyl acetal, diallyl phthalate polymer, phenol resin, epoxy resin, silicone resin, polysulfone resin, or A binder resin such as a urea resin may be mixed and used.

  For example, as the low molecular weight host material, compounds represented by the following chemical formulas 34 to 37 may be used. As the polymeric host material, a fluorene polymer, a polyphenylene vinylene polymer, a polyparaphenylene polymer may be used. A polymer having a conjugated double bond such as a polymer may be used. However, the low molecular weight host material and the high molecular weight host material are not limited to the above examples.

Further, when said organic photoelectric child-element compound is used as a host material, the organic photoelectric child element compound may be used alone or may be used with the dopant. The dopant is a compound having a high light-emitting ability by itself and is usually used in a small amount mixed with the host, so that it is also called a guest. In other words, the dopant is a substance that emits light when doped with a host substance, and generally a substance such as a metal complex that emits light by multiplet excitation that excites the triplet state or higher is used. As such a dopant, red (R), green (G), blue (B), and white (W) fluorescent or phosphorescent dopants commonly used in the art can be used. It is preferred to use a blue or white phosphorescent dopant. Alternatively, a material that has high luminous efficiency, does not easily aggregate, and is uniformly distributed in the host material may be used.

Examples of the phosphorescent dopant include an organometallic compound containing an element that is Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. Is mentioned. More specifically, red phosphorescent dopants include platinum-octaethylporphyrin complex (PtOEP), Ir (btp) ₂ (acac) (bis (2- (2′-benzothienyl) -pyridinato-N, C3 ′) iridium (Acetylacetonate)), Ir (Piq) ₂ (acac), Ir (Piq) ₃ , RD61 from UDC, etc. may be used, and as the green phosphorescent dopant, Ir (PPy) ₂ (acac), Ir (PPy) ₃ , GD48 manufactured by UDC may be used, and (4,6-F ₂ PPy) ₂ Irpic, flrpic (iridium bis [4,6-di-fluorophenyl)- Pyridinato-N, C2 ′] picolinate) and the like may be used. Here, Piq means 1-phenylisoquinoline, acac means acetylacetonate, and PPy means 2-phenylpyridine.

Moreover, the organic photoelectric child element compound according to an embodiment of the present invention, the thermal decomposition temperature (T _d) may be 350 to 600 ° C.. Thus, the organic photoelectric child element compound according to an embodiment of the present invention can be used as a host material or a charge transport material having excellent thermal stability. Therefore, it is possible to improve the life characteristics of the organic photoelectric child elements.

According to another embodiment of the present invention, the anode comprises a cathode, and an organic thin film layer disposed between the anode and the cathode, the organic thin film layer, an organic light electronic device according to an embodiment of the present invention the organic light electronic device comprising the use compound. At this time, the organic light electronic device, organic light emitting diodes, organic solar cells, organic transistors, organic photosensitive drum, and an organic memory device. If organic solar cells, organic light electronic elements for compounds according to an embodiment of the present invention is contained in the electrode or the electrode buffer layer, whereby it is possible to improve the quantum efficiency, in the case of the organic transistor, the gate It can be used as an electrode material in source-drain electrodes and the like.

The organic thin film layer may include an organic photoelectric child element compound, light-emitting layer, a hole blocking layer, electron transport layer (ETL), electron injection layer (EIL), hole injection layer (HIL), a hole It may be a transport layer (HTL), an electron blocking layer, or a combination thereof.

Hereinafter, the organic light emitting diode will be described in detail.

Figures 1-5 are cross-sectional views of an organic light emitting diode including the organic photoelectric child element compound.

1 to 5, the organic light emitting diodes 100, 200, 300, 400, and 500 have a structure including at least one organic thin film layer 105 disposed between the anode 120 and the cathode 110. .

The substrate used in the organic light emitting diode is not particularly limited in the field, but more specifically, a glass substrate, a transparent plastic substrate, etc. that are excellent in transparency, surface smoothness, ease of handling, and waterproofness. A substrate can be used.

The anode 120 includes a material having a high work function so as to facilitate hole injection into the organic thin film layer. Specific examples of the anode material include metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold, or alloys of these metals; zinc oxide, indium oxide, indium tin oxide (ITO), indium Metal oxides such as zinc oxide (IZO) and the like; metal oxides such as ZnO / Al, SnO ₂ / Sb, and composite metals can be used. However, the anode is not limited to the above substance. More specifically, the anode may be a transparent electrode containing ITO.

The cathode 110 preferably includes a material having a low work function so as to facilitate electron injection into the organic thin film layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or alloys thereof; Examples thereof include multilayer structure materials such as LiF / Al, LiO ₂ / Al, LiF / Ca, LiF / Al, BaF ₂ / Ca, and the like. However, the cathode is not limited to the above substances. More specifically, the cathode may be a metal electrode such as aluminum.

First, FIG. 1 illustrates an organic light emitting diode 100 in which only the light emitting layer 130 exists as the organic thin film layer 105.

FIG. 2 shows a two-layer organic light emitting diode 200 having a light emitting layer 230 including an electron transport layer (ETL) and a hole transport layer (HTL) 140 as the organic thin film layer 105. In this case, the light emitting layer 130 functions as an electron transport layer (ETL), and the hole transport layer (HTL) 140 functions to improve the bonding property with a transparent electrode such as ITO and the hole transport property.

The hole transport layer (HTL) 140 is commonly used in the art and is not particularly limited in type. For example, the hole transport layer (HTL) 140 may be a poly (styrene sulfonate) (PSS) layer doped with a poly (styrene (PSS) layer. 3,4-ethylenedioxy-thiophene) (PEDOT) (PEDOT: PSS), N, N′-bis (3-methylphenyl) -N, N′-diphenyl- [1,1′-biphenyl] -4, 4'-diamine (TPD), N, N'- di (1-naphthyl) -N, N'-diphenyl henge Jin (NPB) to be used in conjunction with organic photoelectric child element compound according to an embodiment of the present invention such as Can do. However, the hole transporting substance is not limited to the above substance.

FIG. 3 shows a three-layer organic light emitting diode 300 having an electron transport layer (ETL) 150, a light emitting layer 130, and a hole transport layer (HTL) 140 as the organic thin film layer 105. Reference numeral 130 is an independent form, and shows a form in which a film excellent in electron transporting property and hole transporting property is laminated in a separate layer.

The electron transport layer (ETL) 150 is generally used in the art and is not particularly limited. For example, aluminum tris (8-hydroxyquinoline) (Alq ₃ ); 2- (4-biphenyl-5 -1,3,4-oxadiazole derivatives such as phenyl-1,3,4-oxadiazole (PBD); 1,3,4-tris [(3-phenyl-6-trifluoromethyl) quinoxaline- 2-yl] quinoxaline derivative such as benzene (TPQ);. and triazole derivatives such as may be used with an organic photoelectric child element compound according to an embodiment of the present invention, however, the electron transporting material is limited to the material Not.

FIG. 4 shows a four-layer organic light emitting diode 400 in which an electron injection layer (EIL) 160, a light emitting layer 130, a hole transport layer (HTL) 140, and a hole injection layer (HIL) 170 exist as the organic thin film layer 105. In the drawing, the hole injecting layer (HIL) 170 can improve the bonding with ITO used as a cathode.

FIG. 5 shows that the electron transport layer (ETL) 150, the light emitting layer 130, the hole transport layer (HTL) 140, and the hole injection layer (HIL) 170 as the organic thin film layer 105 further include an electron injection layer (EIL) 160. it is a view showing a 5-layer type organic light-emitting diode 500, the organic light emitting diode 500 is effective for a reduction in voltage.

  The light emitting layers 130 and 230 may have a thickness of 5 to 1000 nm, and the hole transport layer (HTL) 140 and the electron transport layer (ETL) 150 may each independently have a thickness of 10 to 10 nm. It may be 10,000cm. However, the thickness range is not limited.

1 to 5, the electron transport layer (ETL) 150, the electron injection layer (EIL) 160, the light emitting layers 130 and 230, the hole transport layer (HTL) 140, the hole injection layer ( HIL) 170 or may be included organic photoelectric child element compound according to an embodiment of the present invention to a combination thereof. At this time, the organic photoelectric child element compound, the electron transport layer (ETL) 0.99 or an electron injection layer (EIL) 160 may be used in the electron transport layer (ETL) 0.99 containing, electron-transporting layer among them (ETL ), It is not necessary to form a hole blocking layer separately, and thus an organic light emitting diode having a more simplified structure can be provided.

Further, when said organic photoelectric child-element compounds are included in the light emitting layer 130 and 230, the organic photoelectric child element compound is used as the phosphorescent host obtained, the light emitting layer 130, 230 may further include a dopant . At this time, the dopant may be a red, green, blue, or white phosphorescent dopant.

The organic light-emitting diode described above is formed by forming an anode on a substrate, and then forming a dry film formation method such as vacuum deposition, sputtering, plasma plating, ion plating, etc .; After the organic thin film layer is formed by a film method or the like, the cathode may be formed thereon for manufacturing.

According to still another embodiment of the present invention, a display device including the organic light emitting diode is provided.

  The invention is explained in more detail using the following implementation. However, these examples are exemplary embodiments and the present invention is not limited.

(Synthesis of organic photoelectric child element compound)
Example 1
The organic photoelectric child element compound was synthesized in Scheme 1 of the following methods.

First Step: Synthesis of Intermediate Product (B) In a 500 mL round bottom flask equipped with a thermometer, reflux condenser and stirrer in an argon atmosphere, 11.0 g (24.7 mmol) of compound A, 1-bromo-2-nitrobenzene 0 g (29.7 mmol), 1 g (0.86 mmol) of tetrakistriphenylphosphine palladium, and 200 mL of tetrahydrofuran were mixed, 50 mL of 2M potassium carbonate was added to the mixed solution, and the mixture was stirred at 75 ° C. for 24 hours.

  After cooling to room temperature to complete the reaction of the reactant, it was extracted with methylene chloride and washed with water. Then, the water | moisture content of the reaction material was removed with anhydrous magnesium sulfate, and the organic solvent was removed by filtering. The final residue was purified by silica gel chromatography using a mixed solvent of methylene chloride and hexane (volume ratio 1: 1) to obtain 9 g of intermediate product (B) (yield: 82.7%).

Second stage: Synthesis of intermediate product (C) 8 g (18.2 mmol) of the intermediate product (B) synthesized in the first stage and 14.3 g (54.6 mmol) of triphenylphosphine were added to 150 ml of dichlorobenzene. And heated to reflux at 160 ° C. under an argon atmosphere.

  The organic solvent was removed by distillation under reduced pressure, followed by extraction with methylene chloride and washing with water. Then, the organic solvent was removed by removing the water | moisture content of the reaction material with the anhydrous magnesium sulfate, and filtering the wash | cleaned reaction material. The final residue was purified by silica gel chromatography using a mixed solvent of methylene chloride and hexane (volume ratio 2: 1) to obtain 5.3 g of intermediate product (C) (yield: 71.5%). It was.

Stage 3: After dissolving intermediate product synthesized in Synthesis said second stage of the organic light electronic elements for compound (C) 5g (12.2mmol) in anhydrous tetrahydrofuran 100 mL, in 1.6M at -78 ° C. 9.2 mL of n-BuLi was gradually added dropwise and stirred for 30 minutes. Next, the mixture was further stirred at room temperature for 20 minutes, mixed again with 1.32 g (5.8 mmol) of 2,4-dichloro-6-phenyltriazine at −78 ° C., and stirred at room temperature for 12 hours.

After cooling to room temperature to complete the reaction of the reactant, it was extracted with methylene chloride and washed with water. Then, the water | moisture content of the reaction material was removed with anhydrous magnesium sulfate, and the organic solvent was removed by filtering. The final residue was mixed solvent (volume ratio 1: 3) of methylene chloride and hexane and purified by silica gel chromatography using, recrystallized organic photoelectric child element compound 2.7 g (yield: 48.0% )

As a result of analyzing the obtained organic photoelectric child element compound by elemental analysis is as follows.

Calculated value C, 88.08; H, 4.68, N, 7.23
Found C, 88.10; H, 4.66, N, 7.23
Example 2
The organic photoelectric child element compound was synthesized in Scheme 2 the following methods.

First Step: Synthesis of Intermediate Product (E) 10.0 g (22.5 mmol) of compound D, 1-bromo-2-nitrobenzene in a 500 mL round bottom flask with thermometer, reflux condenser, and stirrer in an argon atmosphere. 45 g (27.0 mmol), 1 g (0.86 mmol) of tetrakistriphenylphosphine palladium and 200 mL of tetrahydrofuran were mixed, and 50 mL of 20% tetratriethylammonium hydroxide was added to the mixed solution, and then at 75 ° C. for 24 hours. Stir.

  After cooling to room temperature to complete the reaction of the reactant, it was extracted with methylene chloride and washed with water. Then, the water | moisture content of the reaction material was removed with anhydrous magnesium sulfate, and the organic solvent was removed by filtering. The final residue was purified by silica gel chromatography using a mixed solvent of methylene chloride and hexane (volume ratio 1: 1) to obtain 7.8 g of intermediate product (E) (yield: 78.8%). It was.

Second Step: Synthesis of Intermediate Product (F) 7 g (15.9 mmol) of the intermediate product (E) synthesized in the first step and 14.3 g (54.6 mmol) of triphenylphosphine were added to 150 ml of dichlorobenzene. And heated to reflux at 160 ° C. under an argon atmosphere.

  The organic solvent was removed by distillation under reduced pressure, followed by extraction with methylene chloride and washing with water. Thereafter, the water content of the reaction product washed with anhydrous magnesium sulfate was removed, and the organic solvent was removed by filtration. The final residue was purified by silica gel chromatography using a mixed solvent of methylene chloride and hexane (volume ratio 2: 1) to obtain 4.4 g of intermediate product (F) (yield: 68%).

Stage 3: After dissolving intermediate product synthesized in Synthesis said second stage of the organic light electronic elements for compound (F) 4g (9.8mmol) in anhydrous tetrahydrofuran 100 mL, in 1.6M at -78 ° C. 9.2 mL of n-BuLi was gradually added dropwise and stirred for 30 minutes. Next, the mixture was further stirred at room temperature for 20 minutes, again mixed with 1 g (4.4 mmol) of 2,4-dichloro-6-phenyltriazine at −78 ° C., and stirred at room temperature for 12 hours.

After cooling to room temperature to complete the reaction of the reactant, it was extracted with methylene chloride and washed with water. Then, the water | moisture content of the reaction material was removed with anhydrous magnesium sulfate, and the organic solvent was removed by filtering. The final residue mixed solvent of methylene chloride and hexane (volume ratio 1: 3) was purified by silica gel chromatography using, recrystallized organic photoelectric child element compound 1.8 g (yield: 42.3% )

As a result of analyzing the obtained organic photoelectric child element compound by elemental analysis is as follows.

Calculated value C, 88.08; H, 4.68, N, 7.23
Found C, 88.06; H, 4.70, N, 7.23
(Manufacture of organic light emitting diodes)
Example 3
An organic light emitting diode was fabricated using the compound synthesized in Example 1 as a host and Ir (PPy) ₃ as a dopant. ITO was used as the anode with a thickness of 1000 mm, and aluminum (Al) was used as the cathode with a thickness of 1500 mm.

Specifically, a method of manufacturing an organic light emitting diode will be described. An anode is formed by cutting an ITO glass substrate having a sheet resistance value of 15 Ω / cm ² into a size of 50 mm × 50 mm × 0.7 mm, and acetone and isopropyl alcohol. After ultrasonic cleaning for 15 minutes in pure water, UV ozone cleaning was performed for 30 minutes.

N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (NPB) (NPB) under the conditions of a vacuum degree of 650 × 10 ⁻⁷ Pa and a deposition rate of 0.1 to 0.3 nm / s on the substrate. 70 nm) and 4,4 ′, 4 ″ -tri (N-carbazolyl) triphenylamine (TCTA) (10 nm) were deposited to form an 800 正 孔 hole transport layer (HTL).

Next, a light-emitting layer having a thickness of 300 mm was formed using the compound synthesized in Example 1 under the same vacuum deposition conditions. At this time, Ir (PPy) ₃ as a phosphorescent dopant was simultaneously deposited. At this time, the deposition rate of the phosphorescent dopant was adjusted, and when the total amount of the light emitting layer was 100% by weight, the phosphorescent dopant was deposited so that the total amount was 10% by weight.

  Bis (8-hydroxy-2-methylquinolinato) -aluminum biphenoxide (BAlq) was deposited on the light emitting layer using the same vacuum deposition conditions to form a hole blocking layer having a thickness of 50 mm.

Next, Alq ₃ was deposited under the same vacuum deposition conditions to form an electron transport layer (ETL) having a thickness of 200 mm.

  An organic light emitting diode was manufactured by sequentially depositing LiF and Al as a cathode on the electron transport layer (ETL).

The organic light emitting diode is ITO / NPB (70 nm) / TCTA (10 nm) / EML (the compound of Example 1 (90 wt%) + Ir (PPy) ₃ (10 wt%), 30 nm) / Balq (5 nm) / Alq. ₃ (20 nm) / LiF (0.5 nm) / Al (150 nm).

Comparative Example 1
The same method as in Example 3 except that 4,4′-N, N′-dicarbazole biphenyl (CBP) was used as the host of the light emitting layer instead of the compound synthesized in Example 1. Made an organic light-emitting diode.

Experimental Example 1: Performance Evaluation of Organic Light-Emitting Diode The organic light-emitting diode manufactured in Example 3 and Comparative Example 1 was measured for changes in current density, luminance, and luminous efficiency due to voltage. The specific measurement method is as follows, and the results are shown in Table 1 below.

(1) Measurement of change in current density due to voltage change The current value is measured using a current-voltmeter (Keithley 2400) while increasing the voltage from 0 V to 10 V, and the measured current value is divided by the area to obtain the current. Density was calculated. The results are shown in FIG.

(2) Measurement of luminance change due to voltage change For the manufactured organic light emitting diode, the luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0V to 10V, and the result was obtained. It was. The results are shown in FIG.

(3) Measurement of luminous efficiency Current efficiency (cd / A) and power efficiency of the same brightness (2000 cd / m ² ) using the luminance, current density and voltage measured in (1) and (2) above (Lm / W) was calculated. The results are shown in FIGS.

(4) Color coordinates Color coordinates were measured using a luminance meter (Minolta Cs-100A), and the results are shown in Table 1 below.

  Referring to Table 1, as a result of evaluating the characteristics of the organic light emitting diode, the organic light emitting diode manufactured in Example 3 has a lower driving voltage than the organic light emitting diode of Comparative Example 1, and has extremely high current efficiency and power efficiency. It was confirmed that the device performance was improved. It was confirmed that the compound according to Example 1 lowered the driving voltage of the organic light emitting diode and improved the luminance and efficiency.

  Although the present invention has been described based on the presently considered embodiments, the present invention is not limited to the embodiments described above, and various modifications and equivalent forms included in the spirit and scope of the claims. Can be done. Therefore, it should be understood that the above examples are illustrative and do not limit the invention in any way.

100, 200, 300, 400, 500 organic light emitting diodes ,
105 organic thin film layer,
110 cathode,
120 anode,
130 light emitting layer,
140 hole transport layer (HTL),
150 electron transport layer (ETL),
160 electron injection layer (EIL),
170 hole injection layer (HIL),
230 Light emitting layer + electron transport layer (ETL).

Claims (11)

Compound for organic optoelectronic device to which substituents represented by the following chemical formula 1 and chemical formula 2 are bonded :
In Formulas 1 and 2,
L is a divalent linking group, which is substituted or unsubstituted with a C1 to C30 alkyl group or a C6 to C30 aryl group, and contains only 1 to 3 nitrogen atoms as C2 to C30. A heteroarylene group of
R ¹ and R ² are the same or different from each other, and each independently represent a C1-C30 alkyl group or a C6-C30 aryl group substituted or unsubstituted C6-C30 aryl group ,
R ^{3 to} R ⁵ are all hydrogen,
a is 2 . The compound for an organic optoelectronic device according to claim 1, wherein the chemical formula 1 is represented by the following chemical formula 1a:
In Formula 1a,
Ra ¹ and Ra ² are all hydrogen,
R ³ is hydrogen. The chemical formula 2 is represented by any one of the following chemical formulas 2a to 2c, and the compound for an organic optoelectronic device according to claim 1 or 2 :
In the chemical formulas 2a to 2c,
L is a divalent linking group, which is substituted or unsubstituted with a C1 to C30 alkyl group or a C6 to C30 aryl group, and contains only 1 to 3 nitrogen atoms as C2 to C30. A heteroarylene group of
R ⁴ and R ⁵ are all hydrogen,
a is 2 . The compound for organic optoelectronic devices according to any one of claims 1 to 3, wherein L in the chemical formula 2 is a divalent linking group derived from a compound represented by the following chemical formula 2e:
In Formula 2e,
Q ¹ to Q ⁶ are the same or different from one another, each independently, an N atom or a substituted or unsubstituted C atom, when this, the substitution, aryl of C6~C30 Motodea ^is, 1-3 of Q 1 to Q ⁶ is a N atom, the remainder being C atoms. The compound for organic optoelectronic devices according to any one of claims 1 to 4, wherein L in the chemical formula 2 is represented by any one of the following chemical formulas L4 to L21:
The compound for organic optoelectronic devices according to claim 1, represented by any one of the following chemical formulas 3 to 8:
In the chemical formulas 3 to 8,
L is a C2 to C30 heteroarylene group containing only 1 to 3 nitrogen atoms as a heteroatom, substituted or unsubstituted with a C1 to C30 alkyl group or a C6 to C30 aryl group ,
R ¹ , R ² , R ⁶ and R ⁷ are the same or different from each other, and each independently represents a C1-C30 alkyl group substituted or unsubstituted with a C1-C30 alkyl group or a C6-C30 aryl group. An aryl group of C30,
R ^{3 to} R ⁵ and R ^{8 to} R ¹⁰ are all hydrogen. The compound for organic optoelectronic devices according to claim 1, which is represented by any one of the following chemical formula 9 to chemical formula 21 and chemical formula 30 to chemical formula 32:
The compound for an organic optoelectronic device according to any one of 請 Motomeko 1-8, for use as charge transport material or a host material. An anode; a cathode; and at least one organic thin film layer disposed between the anode and the cathode;
Wherein said at least one organic thin film layer comprises a compound for an organic optoelectronic device according to any one of claims 1 to 7 OLED. The organic thin film layer includes a light emitting layer, a hole blocking layer, an electron transport layer (ETL), an electron injection layer (EIL), a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer, or these The organic light emitting diode according to claim 9 , which is a combination. To claim 9 or 10 including the organic light emitting diode according display device.